The quest for a triplet ground-state alkene: Highly twisted C═C double bonds
Wu JI, van Eikema Hommes N, Lenoir D, Bachrach SM (2019)
Publication Type: Journal article
Publication year: 2019
Journal
Book Volume: 32
Article Number: e3965
Journal Issue: 9
DOI: 10.1002/poc.3965
Abstract
Density functional theory and extrapolated CCSD(T) computations of several “anti-Bredt” alkenes were carried to explore possible 1,2-diyl “alkene” candidates with a triplet ground state. Ten candidates containing twisted double bonds at the bridgehead positions of bicyclic structures (1-6) or adamantene (7-10) derivatives were studied. Based on a combination of ring strain, rigid scaffolding, and steric crowding, four species were identified to have surprisingly low singlet-triplet energy gaps (lower than 4 kcal/mol). A tert-butyl substituted bicyclic structure (4) was identified to have a near-zero singlet-triplet energy gap, but no triplet ground-state alkene was found. Ring strain energy (RSE) calculations, π-orbital axis vector (POAV) analyses, and multiple linear regression models were performed to elucidate the geometric and energetic effects of double bond twisting in 1-10. Based on our computational exploration, it appears unlikely that there is a ground-state triplet olefin.
Authors with CRIS profile
Involved external institutions
University of Houston
United States (USA) (US)
Monmouth University
United States (USA) (US)
Helmholtz Zentrum München - Deutsches Forschungszentrum für Gesundheit und Umwelt (HMGU) / Helmholtz Munich
Germany (DE)
United States (USA) (US)
Monmouth University
United States (USA) (US)
Helmholtz Zentrum München - Deutsches Forschungszentrum für Gesundheit und Umwelt (HMGU) / Helmholtz Munich
Germany (DE)
How to cite
APA:
Wu, J.I., van Eikema Hommes, N., Lenoir, D., & Bachrach, S.M. (2019). The quest for a triplet ground-state alkene: Highly twisted C═C double bonds. Journal of Physical Organic Chemistry, 32(9). https://doi.org/10.1002/poc.3965
MLA:
Wu, Judy I., et al. "The quest for a triplet ground-state alkene: Highly twisted C═C double bonds." Journal of Physical Organic Chemistry 32.9 (2019).
BibTeX: Download